CA2036488C - A process for the production of fillers modified with organosilicon compounds, the fillers thus modified and their use - Google Patents
A process for the production of fillers modified with organosilicon compounds, the fillers thus modified and their use Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
A process for the production of fillers modified with organosilicon compounds, the fillers thus modified and their use.
The invention relates to a two-step process for the surface modification of natural or synthetic oxidic or silicate fillers using organosilicon compounds correspond-ing to the following formulae (see formulae I or II) in which the filler and the compound are intensively mixed in the absence of further solvent and the homogenized mixture is subjected to the hydrophobicizing reaction in the preheated mixer.
The invention relates to a two-step process for the surface modification of natural or synthetic oxidic or silicate fillers using organosilicon compounds correspond-ing to the following formulae (see formulae I or II) in which the filler and the compound are intensively mixed in the absence of further solvent and the homogenized mixture is subjected to the hydrophobicizing reaction in the preheated mixer.
Description
'i'loi:inveut.i.on relates to processes for the production of sLorahle, natural or syr7thet:i.c, oxidic or silicate fillers modified with organosilicon compounds, to the fillers thus modified and to their use in vulcanizable rubber mixtures.
It is known that oxidic surfaces can be pretreated with organosilicon compounds to improve the bond between the oxidic fi:ll.er and organic polymers differ9.ng widely in their chemical composition and hence to improve the rein-forcing properties of the fillers in the pol~~mers.
This pretreatment may be carried out, for example, by dissolving the particular organosilicon compound in an organic solvent and treating clays, for example, with the resulting solution (US- 3,227,675). It is known from US-3,567,680 that kaolins suspended in water can be modi-fied with mercapto- and aminosilanes. However, the organo-silicon compounds in question are soluble in water in the quantities required for the modification, so that in this case, too, the filler is treated from a solution. US-4,151,154 relates to oxidic silicate fillers of which the surface 9.s exposed to a treatment with two types of organosilicon compounds.
The oxidic particles era treated in such a way that they have a greater affinity for water and are also easier to disperse in aqueous systems. The use of sulfur-contain ing organosilicon compounds in vulcanizable rubber mixtures is known from US- 4,076,550. This compound may also be used in the form of mixtures with silica, although the mixtures a.re not thermally pretreated and have a limited storage life. EP- 0 226 871 describes a process in which the surface of silicate fillers is modified with an aqueous emulsion of water-insoluble organosilicon compounds. US-4,141,751 relates to a process which does not use any solvent whatever, but which has been found in practice to be impracticable for certain organosilicon compounds.
_1_ According to one a=~pect, the invention provides a process for the surface modification of natural or synthetic oxidic or silicate fillers using one or more organosilicon compounds corresponding to formula (I) (Rln (RD) 3-nsl- (Alk) in- (Ar) p~ q ~B~ ( I ) in which B represents -SCN (where q = 1) or -SX- (where q = 2), R and R1 may be the same or different and represent a C1-4 alkyl group or the phenyl radical, in addition to which R may be a Cl_4-alkyl-Ca_:,~-alkoxy group, n is 0, 1 or 2, Alk is a difunctional, linear or branched hydrocarbon radical containing 1 to 6 carbon atoms, m is 0 or 1, Ar is a C6_,2 arylene radical, p is 0 or l, with the proviso that p and m cannot both be 0 and x is a number of 2 to 8, wherein a) at least one organosilicon compound corresponding to formula I is intensively mixed with the filler at temperatures below 60°C in a concentration of 1 x 10-' to 3.5 x 10-6 mol trialkoxysilyl groups per square meter filler surface, to form a homogenized mixture, and b) the homogenized mi:~ture is then subjected to a hydrophobicizing reaction in a preheated mixer, in a constant-temperature bed or in any other suitable heatable reaction vessel at a temperature in the range from 60 to 160° C and preferably ai.. a temperature in the range from 80 to 140°C. The residence time in the reaction vessel is generally from 3 minute; to 2.4 hours.
According to another aspect, the invention provides a method for the surface-modification of natural or synthetic, oxide or silicate filler: having surface -OH groups using one or more organosilicon compounds of the Formula I:
(Rln (RO) 3_nSl- (Alk) mw (Ar) p) q (B~ ( I ) in which:
B represents -SCN (if q=1) or -SX- (if q=2) , R signifies an alkyl croup with 1 to 4 carbon atoms, the phenyl group, or a Cl-C4 alkyl-C1-C4 alkoxy group, R1 signifies an alkyl group with 1 to 4 carbon atoms or the phenyl group, n represents 0, 1 and 2, Alk signifies a bivalent, straight or branched hydrocarbon group having 1 to 6 carbon atoms, m represents 0 or l, Ar is an arylene group with 6 to 12 carbon atoms, p is 0 or 1, with the provision that p and m do not signify 0 simultaneously, and x is a number from 2 t:o 8, the method comprising:
a) intensively mixing at least one organosilicon compound according to Formula I with the filler, but without the addition of further solvents, at a temperature below 60°C in a concentration of up to 3.5 x 10-~ moles trialkoxysilyl groups per one square meter filler surface to form a homogenized mixture, and b) subsequently subjecting the homogenized mixture to a hydrophobing reaction at temperature greater than 60°C.
The intensive mixer used is, for example, a plough-shares mixer of which tree rotational speed is adjusted in such a way that intensive mixing is obtained without 3a destroying the structure' of, for example, the finely divided silicas used, and the temperature also remains below 60°C.
In general, the temperature may be between 20° and < 60°C
while the preheating temperature may be at least 60°C.
The natural and synthetic fillers to be modified and also mixtures of two or more of these fillers are known per se in rubber technology. The main preferred precondition for their suitability i:~ the presence of OH groups at the surface which are capab7_e of reacting with the alkoxy groups of the organosilicon compounds. The fillers are oxidic and silicate compounds which are compatible with rubbers and which have the particle fineness required for this purpose.
Particularly suitable natural silicates are kaolins or clays, although kieselguhr or diatomaceous earths may also be used.
Oxidic fillers are, for example, aluminium oxide, aluminium hydroxide or t~rihydrate and titanium dioxide obtained from natural sources.
Particularly suitable synthetic fillers are aluminium silicates, silicates, precipitated and pyrogenic silicas having BET surfaces (as measured with gaseous nitrogen) in the range from 1 to 1000 m2/g and more particularly up to 300 mz/g.
The fillers modified in accordance with the invention contain up to 3.5 x 10-6 mol trialkoxysilyl groups per square meter filler surf=ace and preferably from 0.1 x 10-6 to 3.5 x 10-6 mol. They are particularly suitable for use in vulcanizable and moldable rubber mixtures produced by any of the methods typically used in the rubber industry.
Suitable rubbers include rubbers which can be cross-linked with sulfur and vulcanization accelerators) to form an elastomers and mixtures of such rubbers. These rubbers are, in particul<~r, the halogen-free rubbers, preferably so-called dime c:l.aistomers. Rubbers of this 'type include, for example, oil-extended, natural and synthetic rubbers, such as natural. rubbers, butadiene rubbers, isoprene rubbers, butadiene-styrene rubbers, butadiene-acrylonitrile rubbers, butyl rubbers, terpolymers of ethylene, propylene and unconjugated dimes. 'fhe following additional rubbers may be used for rubber mixtures with the rubbers mentioned:
carboxyl rubbers, epoxy rubbers, traps-polypentenamer, halogenated butyl rubbers, rubbers of ?,--chlorobutadiene, ethylene/vinyl acetate copolymers, ethylene/propylene co-polymers and, optionally, chemical derivatives of natural rubber and modified natural rubbers.
It is of course important to keep to the prescribed total filler content in the vulcanizable rubber mixture.
In other words, the filler to be used may be both com pletely and also partly modified. In the latter case, however, the remainder maybe subsequently incorporated in unmodified form.
The fillers modified in accordance with the invention have the advantage of high stability in storage over the pure mixtures of, for example, bis-(3-triethoxysilyl-propyl)-tetrasulfane with silica which are known from US-PS 4,076,550.
They have the advantage over the in situ process used for years in the rubber industry-direct addition of silane to carbon black and/or silicate-filled rubber mixtures of a low water content, a higher compacted bulk density in relation to untreated filler, easier storage and, in addition, better processing behavior for the user in the rubber-processing industry (homogeneous mixture prepara-tion, saving of mixing steps and mixing times). The fillers modified in accordance with the invention cannot be produced by the process described in US 4,141,751. If a bis-(3-trial)caxysilylpropyl)-tetrasulfane is mixed with _4_.
~~ i~~~~
a filler and if energy is S.ntroduced into the resulting mixture by intensive stirring, as described above, to such a degree that tyre hydrophobicizing reaction takes place under the effect of the resu7.t.ing constant increase in temperature, the end product obtained is lumpy. However, a free-flowing, :finely divided product, such as produced in accordance with the invention, is desirable.
Metlroxy group determinations were carried out on the modified fillers produced in accordance with the invention (F. Viebock and J1. Schwabach, Chem. I3er. G3, (1930) 2818) .
After the total hydrophobicization of precipitated silica of the ULTRASIL~ VN 2 type (125 m2/g) or ULTRASIL~
VN 3 type (175 m'/g) with 1.75~106 mol Si 167/mz, based on the silica, the following values are obtained fox the number of free methoxy groups still present (of the six originally present per molecule):
Process according to the invention VN 2/Si 167 1.7 VN 3/Si 167 2.5 The storable modified fillers produced in accordance with the preferred embodiment of the invention lead to a distinct improvement in the rubber properties of the vulcanized rubber mixtures in relation to mixtures without the modified fillers, Stability in storage is evaluated by determination of the polysulfide content over a period of 12 months at 50°C
(Table 5); within the accuracy of measurement, the varia tions are minimal.
By contrast, the reaction of mercaptosilana and silicate filler carried out at the same time in accordance with US- 4,141,751 leads to products which vary con-siderably in their total sulfur content (Table 4) which is indicative of inadequate stability in storage.
_5-~ 90 116 KV
The process according to the invention may be carried out both discontinuously and continuously. The products obtained have the same properties.
The following Examples illustrate the production process and pravide an insight into the favorable proper ties of the vulcanizates abtained using the modified fillers produced in accordance with the invention.
The polysulfidic organosilicon compound used and the other compounds are the following products:
Polysulfidic organosilicon compounds:
Si 167 - bis-(3-trimethoxysilylpropyl)-tetrasulfane (Degussa) Perbunan~ NS 3307 nitrile/butadiene rubber (NBR) Buna~ Huls styrene/butadiene rubber (SBR) SMR 5 Standard Malaysian Rubber (natural rubber) CORAX~ N 220 carbon black, BET surface 120 mz/g (Degussa) Ultrasil~ VN 3 precipitated silica, BET surface m2 /g (Degussa) Naftolen~ ZD: hydrocarbon-based plasticizer Vulkanox~ 4010 NA: N-isopropyl-N'-phenyl-p-phenylenedi-amine Vulkanox~ HS: poly-2,2,4-trimethyl-1,2-dihydroquino-line Frotektor~ antiozonant wax G35:
Vulkacit~ MOZ: N-morpholine-2-benzthiazole sulfenamide Vulkacit~ Mercapto:2-mercaptobenzthiazole Vulkacit~ Thiuram: tetramethyl thiuram monosulfide Vulkacit~ CZ: N-cyclohexyl-2-benzothiazole sulfen-amide PEG 4000: polyethylene glycol MBTS: 2,2'-dibenzothiazolyl disulfide TMTD: tetramethyl thiurarn disulfide KP 140: aliphatic plasticizes Test standards:
The physical tests were carried out at room tempera-ture in accordance with the following standards:
Measured in Tensile strength, elongation DIN 53 504 MPa at break and modulus Tear propagation resistance DIN 53 507 N/mm 1o Shore A hardness DIN 53 505 Mooney value, MT~ 4 DIN 53 524 -Goodrich Flexometer C
(determination of heat ASTM
build up oT) D 623-62 Firestone ball rebound AD 20245 DIN abrasion DIN 53 516 (mm~) Compression set B ASTM 395 D
The production process:
Example 1 4 kg ULTRASIL~ VN 3 (BET surface 7.75 mz/g) are intro-duced into a Henschel F.M. 40 liter mixer equipped with a two-part variant mixing tool with horn, a baffle with a temperature gauge installed in the cover, a vent and a hollow jacket for heating/cooling by steam or water.
1st Step: After the cover has been closed, the mixer is brought to a rotational speed of 2600 r.p.m. 506 g Si 167 are sprayed onto the filler at room temperature ('20-25°C), the mixture is homogenized and is then removed from the mixer. The quantity of silane corresponds to 3.2~10-6 mol trialkoxysilyl groups/m2 surface.
2nd Step: After the mixer has been heated to 120°C, the mixture from step 1 is reintroduced into the mixer which is r then brought to a rotational speed of 2600 r.p.m. After a temperature of 7.40 ° C has been rear_hed, the mixer is switch-ed off and is then emptied after a total residence time of minutes.
The following Tables show the measured values obtained using the fillers produced in accordance with the invention in various vulcanizates (concentrations expressed in parts by weight).
Example 2 1st Step: Using a differential weigh feeder, ULTRASIL VN 2 (precipitated silica, BET surface 125 mz/g) is introduced into a continuous mixer at a rate of 25 kg/h. At the same time, the silane Si 167 is sprayed onto the silica in the mixer at room temperature from a storage vessel by a piston membrane pump and a disk atomizer at a rate of 2.25 kg/h.
After intensive mixing, the moistened material is dis charged via a screw so that a constant level is maintained in the mixer.
2nd Step: The silica/organosilane mixture discharged from the mixer is pumped into a heated reactor by a membrane pump. The temperature in the reactor is 140°C and the residence time in the reactor is 2 hours, the time in excess of. about 10 to 20 minutes generally being used to remove the alcohol eliminated during the reaction. The product in the reactor is then discharged through a star wheel to maintain a constant level in the reactor. A
storable Ultrasil VN2 modified with bis-(3-trimethoxysilyl-propyl)-tetrasulfane (Si 167) is obtained and is pumped by a membrane pump into a product silo from which it can be subsequently filled into paper sacks.
~~~ ~~~!~
~ yo 116 xV
Table 1 Modified precipitated silica natural.rubber in SMR 5 ML (1-I-4)=70-80 100 100 Ultrasil VN3 40 -Si 167 modif. Ultr.~xsil V2J - 45.08 (corresponds to 5.08 pbw Si per 100 pbw VN 3) Si 167 5.08 -Zinc oxide RS 4 4 Stearic acid 2 2 Naftolen ZD 2 2 Protektor G35 1.5 1.5 Vulkanox HS 1.5 1.5 Vulkanox 4010 NA 1.0 1.0 Vulkacit MOZ 2.82 2.82 Sulfur 2.86 2.86 ML (1+4) at 100C 83 84 Vulcanization temperature:
145C/t9s Tensile strength. (MPa) 18.4 21.3 Modulus, 3000 (MPa) 13.2 13.8 Elongation at break (%) 380 410 Tear propagation resistance (N/mm) 13 15 Ball rebound (%) 63.5 67.5 Shore A hardness 65 65 DIN abrasion (mm3) 146 119 Flexometer (0.175"/108N/30"/RT) DT center (C) 44 41 Static compression (%) 7.7 6.3 Dynamic compression (o) 7.3 5.6 7_0 90 116 KV
Table Modified precipitah.ed silica in SBR 1500 Buna Huls 1500 100 100 Ultrasil VN 2 50 Si 167 modif. Ultrasil VN 2 - 51.5 (corresponds to 3 pbw Si 167 to 100 pbw VN 2) Zinc oxide RS 4 4 Stearic acid 2 2 Vulkacit CZ 2 2 Sulfur 2 2 ML (1+4) at 100C 84 86 Vulcanization temperature 150C/t95 Tensile strength (MPa) 12,8 16.5 Modulus, 300 0 (MPa) 2.6 5.1 Elongation at break (%) 680 590 Tear propagation resistance (N/mm)13 13 Ball rebound (o) 34 37 Shore A hardness 60 64 DTN abrasion (mm3) 192 147 Compression set (22h/70C) 20.2 14.7 Goodrich flexometer (0.175"/108N) Cannot be measured DT center (C) ' 137 Dynamic compression (%) " 10 '.~ ~' i9 ~~~ ~)'..~
.a TabJ.e 3 Modified precipitated silica NI3R
in Perbunan NS 3307 100 100 Ultrasil VN 3 50 -Si 167 modif. Ultrasil VN 3 - 56.4 (corresponds to 12.8 pbw Si per 100 pbw VN 3) Zinc oxide RS 5 5 Stearic acid 2 2 Dioctyl phthalate 10 10 PEG 4000 2.5 2.5 MBTS 1.2 1.2 TMTD 0.6 0.6 Sulfur 1.5 1.5 MLr (1+4) at 100C 78 52 Vulcanization temperature: C/t95 Tensile strength (MPa) 15.1 13.7 Modulus, 200 % (MPa) 2.7 9.2 Elongation at break (%) 630 270 Tear propagation resistance (N/mm) 12 6 Firestone ball rebound (o) 32.8 31.8 Shore .A hardness 66 74 DIN abrasion (mm3) 139 65 Compression set B
22 h/ 70C (%) _ 20.510.9 70 h/100C (%) 51.7 32.7 ~~~~~~~a Stability in storage:
To evaluate the stability in storage of the fillers modified with polysulfidic organosilicon compounds) the following values are determined:
Polysulfide sulfur content of fillers modified with poly-sulfidi.c organosilp.con compounds) during open storage for 12 months at 50°C.
They show a constant polysulfide sulfur content over the entire storage period (Table 5).
By contrast, identical measurements on modified silicas obtained by the process known from US-PS 4,141,751 using 3-mercaptopropyl trimethoxysilane (A 189) show a considerable variation of the sulfur values. This is indicative of inadequate stability of the product obtained in storage (Table a).
1 pbw Si 167/100 pbw VN3 ~ 1~256 10-7mo1 Si 167/m2 1 pbw Si 189/100 pbw VN3 ~ 2~g09 10-7mo1 A 189/m2 13 9~ 116 xv Chemical analysis modified Ultrasil VtJ3_ O~en storage at 50 C
l sul fur t T
~ o .
a TheoreticalStarting 6 Months 12 Months _pb~rr _A189calculated material _ % o ' 100 pbw VN3 1.1 0.151 0.165 0.180 0.213 2.2 0.323 0.336 0.521 0.530 3.3 0.493 0.550 0.731 0.664 3.8 0.576 0.639 0.739 0.742 4.4 0.659 0.747 1.234 1.205 5.5 0.822 0.918 1.393 1.102 8.2 1.219 1.373 1.858 1.783 10.9 1.599 1.864 2.419 2.051 Table 4 Chemical -analysis - Si167 -modified Ultrasil Open storage at 50C
d ~olysulfide sulfur TheoreticalStarting 6 Months 12 Months lbw Si167 calculated material 100 pbw VN3 0 2.5 pbw Si167 0.324 0.339 0.322 0.300 5.4 pbw Si167 0.635 0.684 0.653 0.620 7.6 pbw Si167 0.934 0.964 0.921 0.950 8.9 pbw Si167 1.079 1.135 1.042 1.004 10.1 pbw Si1671.221 1.237 1.219 1.202 12.7 pbw Si1671.497 1.587 1.473 1.402 Table 5 w 14 90 116 KV
Example 3 Silicas modified with 3-thiocyanatopropyl triethoxy-silane (Si 264) are produced in accordance with Examples 1 and 2. The following values are obtained for the free ethoxy groups on the surface (per silane molecule) Table 6 pEW Si 264/100 PBW VN3 Mol Si264/m2 Ethoxy groups 1.34 3 10' 0.65 2.65 7 10' 0.45 4.02 1 106 0.29 5.4 1.4 106 0.23 6.7 1.8 106 0.24 Table 7 pEW Si 264/100 PEW VN2 Mol Si264/m2 Ethoxy groups 1.34 5 . 10_~ . 0.49 2.65 1 106 0.29 4.02 1.5 106 0.24 5.4 2.0 10 6 0.26 6.7 2.5 106 0.30 ... 1 5 9 0 116 ~;V
Table 8 Precip.i.tar~ed silicamodified with Si264in SBR 1500 Buna Hiils 1500 100 100 100 Zn0 RS 3 3 3 Stearic acid 2 2 2 ULTR1~SIL VPI 2 50 - -Si264 mod. VN2 - 50 -(4.82 pbw Si264 to 100 pbw VN2) Si264 mod. VN2 - - 5U
(6.7 pbw Si264 to 1 00 pbw VN2) Vulkaci_t CZ 2 2 2 Sulfur 2 2 2 Rheometer 150°C
Dmax - Dmin ( Nm ) 9 . 7 9 11. 91 12 .
doz (rains.) 19.1 16.3 14.0 tsox (minx,) 40.3 45.9 36.4 tso z ' do x (mlns. ) 24. 3 29. 6 22.4 Vulcanization temperature: 150C/tssz Tensile strength (MPa) 14.3 26.0 25.7 Modulus, 300 (MPa) 3.8 7.3 8.5 Elongation at at break 650 600 560 (o) Shore hardness 66 76 76
It is known that oxidic surfaces can be pretreated with organosilicon compounds to improve the bond between the oxidic fi:ll.er and organic polymers differ9.ng widely in their chemical composition and hence to improve the rein-forcing properties of the fillers in the pol~~mers.
This pretreatment may be carried out, for example, by dissolving the particular organosilicon compound in an organic solvent and treating clays, for example, with the resulting solution (US- 3,227,675). It is known from US-3,567,680 that kaolins suspended in water can be modi-fied with mercapto- and aminosilanes. However, the organo-silicon compounds in question are soluble in water in the quantities required for the modification, so that in this case, too, the filler is treated from a solution. US-4,151,154 relates to oxidic silicate fillers of which the surface 9.s exposed to a treatment with two types of organosilicon compounds.
The oxidic particles era treated in such a way that they have a greater affinity for water and are also easier to disperse in aqueous systems. The use of sulfur-contain ing organosilicon compounds in vulcanizable rubber mixtures is known from US- 4,076,550. This compound may also be used in the form of mixtures with silica, although the mixtures a.re not thermally pretreated and have a limited storage life. EP- 0 226 871 describes a process in which the surface of silicate fillers is modified with an aqueous emulsion of water-insoluble organosilicon compounds. US-4,141,751 relates to a process which does not use any solvent whatever, but which has been found in practice to be impracticable for certain organosilicon compounds.
_1_ According to one a=~pect, the invention provides a process for the surface modification of natural or synthetic oxidic or silicate fillers using one or more organosilicon compounds corresponding to formula (I) (Rln (RD) 3-nsl- (Alk) in- (Ar) p~ q ~B~ ( I ) in which B represents -SCN (where q = 1) or -SX- (where q = 2), R and R1 may be the same or different and represent a C1-4 alkyl group or the phenyl radical, in addition to which R may be a Cl_4-alkyl-Ca_:,~-alkoxy group, n is 0, 1 or 2, Alk is a difunctional, linear or branched hydrocarbon radical containing 1 to 6 carbon atoms, m is 0 or 1, Ar is a C6_,2 arylene radical, p is 0 or l, with the proviso that p and m cannot both be 0 and x is a number of 2 to 8, wherein a) at least one organosilicon compound corresponding to formula I is intensively mixed with the filler at temperatures below 60°C in a concentration of 1 x 10-' to 3.5 x 10-6 mol trialkoxysilyl groups per square meter filler surface, to form a homogenized mixture, and b) the homogenized mi:~ture is then subjected to a hydrophobicizing reaction in a preheated mixer, in a constant-temperature bed or in any other suitable heatable reaction vessel at a temperature in the range from 60 to 160° C and preferably ai.. a temperature in the range from 80 to 140°C. The residence time in the reaction vessel is generally from 3 minute; to 2.4 hours.
According to another aspect, the invention provides a method for the surface-modification of natural or synthetic, oxide or silicate filler: having surface -OH groups using one or more organosilicon compounds of the Formula I:
(Rln (RO) 3_nSl- (Alk) mw (Ar) p) q (B~ ( I ) in which:
B represents -SCN (if q=1) or -SX- (if q=2) , R signifies an alkyl croup with 1 to 4 carbon atoms, the phenyl group, or a Cl-C4 alkyl-C1-C4 alkoxy group, R1 signifies an alkyl group with 1 to 4 carbon atoms or the phenyl group, n represents 0, 1 and 2, Alk signifies a bivalent, straight or branched hydrocarbon group having 1 to 6 carbon atoms, m represents 0 or l, Ar is an arylene group with 6 to 12 carbon atoms, p is 0 or 1, with the provision that p and m do not signify 0 simultaneously, and x is a number from 2 t:o 8, the method comprising:
a) intensively mixing at least one organosilicon compound according to Formula I with the filler, but without the addition of further solvents, at a temperature below 60°C in a concentration of up to 3.5 x 10-~ moles trialkoxysilyl groups per one square meter filler surface to form a homogenized mixture, and b) subsequently subjecting the homogenized mixture to a hydrophobing reaction at temperature greater than 60°C.
The intensive mixer used is, for example, a plough-shares mixer of which tree rotational speed is adjusted in such a way that intensive mixing is obtained without 3a destroying the structure' of, for example, the finely divided silicas used, and the temperature also remains below 60°C.
In general, the temperature may be between 20° and < 60°C
while the preheating temperature may be at least 60°C.
The natural and synthetic fillers to be modified and also mixtures of two or more of these fillers are known per se in rubber technology. The main preferred precondition for their suitability i:~ the presence of OH groups at the surface which are capab7_e of reacting with the alkoxy groups of the organosilicon compounds. The fillers are oxidic and silicate compounds which are compatible with rubbers and which have the particle fineness required for this purpose.
Particularly suitable natural silicates are kaolins or clays, although kieselguhr or diatomaceous earths may also be used.
Oxidic fillers are, for example, aluminium oxide, aluminium hydroxide or t~rihydrate and titanium dioxide obtained from natural sources.
Particularly suitable synthetic fillers are aluminium silicates, silicates, precipitated and pyrogenic silicas having BET surfaces (as measured with gaseous nitrogen) in the range from 1 to 1000 m2/g and more particularly up to 300 mz/g.
The fillers modified in accordance with the invention contain up to 3.5 x 10-6 mol trialkoxysilyl groups per square meter filler surf=ace and preferably from 0.1 x 10-6 to 3.5 x 10-6 mol. They are particularly suitable for use in vulcanizable and moldable rubber mixtures produced by any of the methods typically used in the rubber industry.
Suitable rubbers include rubbers which can be cross-linked with sulfur and vulcanization accelerators) to form an elastomers and mixtures of such rubbers. These rubbers are, in particul<~r, the halogen-free rubbers, preferably so-called dime c:l.aistomers. Rubbers of this 'type include, for example, oil-extended, natural and synthetic rubbers, such as natural. rubbers, butadiene rubbers, isoprene rubbers, butadiene-styrene rubbers, butadiene-acrylonitrile rubbers, butyl rubbers, terpolymers of ethylene, propylene and unconjugated dimes. 'fhe following additional rubbers may be used for rubber mixtures with the rubbers mentioned:
carboxyl rubbers, epoxy rubbers, traps-polypentenamer, halogenated butyl rubbers, rubbers of ?,--chlorobutadiene, ethylene/vinyl acetate copolymers, ethylene/propylene co-polymers and, optionally, chemical derivatives of natural rubber and modified natural rubbers.
It is of course important to keep to the prescribed total filler content in the vulcanizable rubber mixture.
In other words, the filler to be used may be both com pletely and also partly modified. In the latter case, however, the remainder maybe subsequently incorporated in unmodified form.
The fillers modified in accordance with the invention have the advantage of high stability in storage over the pure mixtures of, for example, bis-(3-triethoxysilyl-propyl)-tetrasulfane with silica which are known from US-PS 4,076,550.
They have the advantage over the in situ process used for years in the rubber industry-direct addition of silane to carbon black and/or silicate-filled rubber mixtures of a low water content, a higher compacted bulk density in relation to untreated filler, easier storage and, in addition, better processing behavior for the user in the rubber-processing industry (homogeneous mixture prepara-tion, saving of mixing steps and mixing times). The fillers modified in accordance with the invention cannot be produced by the process described in US 4,141,751. If a bis-(3-trial)caxysilylpropyl)-tetrasulfane is mixed with _4_.
~~ i~~~~
a filler and if energy is S.ntroduced into the resulting mixture by intensive stirring, as described above, to such a degree that tyre hydrophobicizing reaction takes place under the effect of the resu7.t.ing constant increase in temperature, the end product obtained is lumpy. However, a free-flowing, :finely divided product, such as produced in accordance with the invention, is desirable.
Metlroxy group determinations were carried out on the modified fillers produced in accordance with the invention (F. Viebock and J1. Schwabach, Chem. I3er. G3, (1930) 2818) .
After the total hydrophobicization of precipitated silica of the ULTRASIL~ VN 2 type (125 m2/g) or ULTRASIL~
VN 3 type (175 m'/g) with 1.75~106 mol Si 167/mz, based on the silica, the following values are obtained fox the number of free methoxy groups still present (of the six originally present per molecule):
Process according to the invention VN 2/Si 167 1.7 VN 3/Si 167 2.5 The storable modified fillers produced in accordance with the preferred embodiment of the invention lead to a distinct improvement in the rubber properties of the vulcanized rubber mixtures in relation to mixtures without the modified fillers, Stability in storage is evaluated by determination of the polysulfide content over a period of 12 months at 50°C
(Table 5); within the accuracy of measurement, the varia tions are minimal.
By contrast, the reaction of mercaptosilana and silicate filler carried out at the same time in accordance with US- 4,141,751 leads to products which vary con-siderably in their total sulfur content (Table 4) which is indicative of inadequate stability in storage.
_5-~ 90 116 KV
The process according to the invention may be carried out both discontinuously and continuously. The products obtained have the same properties.
The following Examples illustrate the production process and pravide an insight into the favorable proper ties of the vulcanizates abtained using the modified fillers produced in accordance with the invention.
The polysulfidic organosilicon compound used and the other compounds are the following products:
Polysulfidic organosilicon compounds:
Si 167 - bis-(3-trimethoxysilylpropyl)-tetrasulfane (Degussa) Perbunan~ NS 3307 nitrile/butadiene rubber (NBR) Buna~ Huls styrene/butadiene rubber (SBR) SMR 5 Standard Malaysian Rubber (natural rubber) CORAX~ N 220 carbon black, BET surface 120 mz/g (Degussa) Ultrasil~ VN 3 precipitated silica, BET surface m2 /g (Degussa) Naftolen~ ZD: hydrocarbon-based plasticizer Vulkanox~ 4010 NA: N-isopropyl-N'-phenyl-p-phenylenedi-amine Vulkanox~ HS: poly-2,2,4-trimethyl-1,2-dihydroquino-line Frotektor~ antiozonant wax G35:
Vulkacit~ MOZ: N-morpholine-2-benzthiazole sulfenamide Vulkacit~ Mercapto:2-mercaptobenzthiazole Vulkacit~ Thiuram: tetramethyl thiuram monosulfide Vulkacit~ CZ: N-cyclohexyl-2-benzothiazole sulfen-amide PEG 4000: polyethylene glycol MBTS: 2,2'-dibenzothiazolyl disulfide TMTD: tetramethyl thiurarn disulfide KP 140: aliphatic plasticizes Test standards:
The physical tests were carried out at room tempera-ture in accordance with the following standards:
Measured in Tensile strength, elongation DIN 53 504 MPa at break and modulus Tear propagation resistance DIN 53 507 N/mm 1o Shore A hardness DIN 53 505 Mooney value, MT~ 4 DIN 53 524 -Goodrich Flexometer C
(determination of heat ASTM
build up oT) D 623-62 Firestone ball rebound AD 20245 DIN abrasion DIN 53 516 (mm~) Compression set B ASTM 395 D
The production process:
Example 1 4 kg ULTRASIL~ VN 3 (BET surface 7.75 mz/g) are intro-duced into a Henschel F.M. 40 liter mixer equipped with a two-part variant mixing tool with horn, a baffle with a temperature gauge installed in the cover, a vent and a hollow jacket for heating/cooling by steam or water.
1st Step: After the cover has been closed, the mixer is brought to a rotational speed of 2600 r.p.m. 506 g Si 167 are sprayed onto the filler at room temperature ('20-25°C), the mixture is homogenized and is then removed from the mixer. The quantity of silane corresponds to 3.2~10-6 mol trialkoxysilyl groups/m2 surface.
2nd Step: After the mixer has been heated to 120°C, the mixture from step 1 is reintroduced into the mixer which is r then brought to a rotational speed of 2600 r.p.m. After a temperature of 7.40 ° C has been rear_hed, the mixer is switch-ed off and is then emptied after a total residence time of minutes.
The following Tables show the measured values obtained using the fillers produced in accordance with the invention in various vulcanizates (concentrations expressed in parts by weight).
Example 2 1st Step: Using a differential weigh feeder, ULTRASIL VN 2 (precipitated silica, BET surface 125 mz/g) is introduced into a continuous mixer at a rate of 25 kg/h. At the same time, the silane Si 167 is sprayed onto the silica in the mixer at room temperature from a storage vessel by a piston membrane pump and a disk atomizer at a rate of 2.25 kg/h.
After intensive mixing, the moistened material is dis charged via a screw so that a constant level is maintained in the mixer.
2nd Step: The silica/organosilane mixture discharged from the mixer is pumped into a heated reactor by a membrane pump. The temperature in the reactor is 140°C and the residence time in the reactor is 2 hours, the time in excess of. about 10 to 20 minutes generally being used to remove the alcohol eliminated during the reaction. The product in the reactor is then discharged through a star wheel to maintain a constant level in the reactor. A
storable Ultrasil VN2 modified with bis-(3-trimethoxysilyl-propyl)-tetrasulfane (Si 167) is obtained and is pumped by a membrane pump into a product silo from which it can be subsequently filled into paper sacks.
~~~ ~~~!~
~ yo 116 xV
Table 1 Modified precipitated silica natural.rubber in SMR 5 ML (1-I-4)=70-80 100 100 Ultrasil VN3 40 -Si 167 modif. Ultr.~xsil V2J - 45.08 (corresponds to 5.08 pbw Si per 100 pbw VN 3) Si 167 5.08 -Zinc oxide RS 4 4 Stearic acid 2 2 Naftolen ZD 2 2 Protektor G35 1.5 1.5 Vulkanox HS 1.5 1.5 Vulkanox 4010 NA 1.0 1.0 Vulkacit MOZ 2.82 2.82 Sulfur 2.86 2.86 ML (1+4) at 100C 83 84 Vulcanization temperature:
145C/t9s Tensile strength. (MPa) 18.4 21.3 Modulus, 3000 (MPa) 13.2 13.8 Elongation at break (%) 380 410 Tear propagation resistance (N/mm) 13 15 Ball rebound (%) 63.5 67.5 Shore A hardness 65 65 DIN abrasion (mm3) 146 119 Flexometer (0.175"/108N/30"/RT) DT center (C) 44 41 Static compression (%) 7.7 6.3 Dynamic compression (o) 7.3 5.6 7_0 90 116 KV
Table Modified precipitah.ed silica in SBR 1500 Buna Huls 1500 100 100 Ultrasil VN 2 50 Si 167 modif. Ultrasil VN 2 - 51.5 (corresponds to 3 pbw Si 167 to 100 pbw VN 2) Zinc oxide RS 4 4 Stearic acid 2 2 Vulkacit CZ 2 2 Sulfur 2 2 ML (1+4) at 100C 84 86 Vulcanization temperature 150C/t95 Tensile strength (MPa) 12,8 16.5 Modulus, 300 0 (MPa) 2.6 5.1 Elongation at break (%) 680 590 Tear propagation resistance (N/mm)13 13 Ball rebound (o) 34 37 Shore A hardness 60 64 DTN abrasion (mm3) 192 147 Compression set (22h/70C) 20.2 14.7 Goodrich flexometer (0.175"/108N) Cannot be measured DT center (C) ' 137 Dynamic compression (%) " 10 '.~ ~' i9 ~~~ ~)'..~
.a TabJ.e 3 Modified precipitated silica NI3R
in Perbunan NS 3307 100 100 Ultrasil VN 3 50 -Si 167 modif. Ultrasil VN 3 - 56.4 (corresponds to 12.8 pbw Si per 100 pbw VN 3) Zinc oxide RS 5 5 Stearic acid 2 2 Dioctyl phthalate 10 10 PEG 4000 2.5 2.5 MBTS 1.2 1.2 TMTD 0.6 0.6 Sulfur 1.5 1.5 MLr (1+4) at 100C 78 52 Vulcanization temperature: C/t95 Tensile strength (MPa) 15.1 13.7 Modulus, 200 % (MPa) 2.7 9.2 Elongation at break (%) 630 270 Tear propagation resistance (N/mm) 12 6 Firestone ball rebound (o) 32.8 31.8 Shore .A hardness 66 74 DIN abrasion (mm3) 139 65 Compression set B
22 h/ 70C (%) _ 20.510.9 70 h/100C (%) 51.7 32.7 ~~~~~~~a Stability in storage:
To evaluate the stability in storage of the fillers modified with polysulfidic organosilicon compounds) the following values are determined:
Polysulfide sulfur content of fillers modified with poly-sulfidi.c organosilp.con compounds) during open storage for 12 months at 50°C.
They show a constant polysulfide sulfur content over the entire storage period (Table 5).
By contrast, identical measurements on modified silicas obtained by the process known from US-PS 4,141,751 using 3-mercaptopropyl trimethoxysilane (A 189) show a considerable variation of the sulfur values. This is indicative of inadequate stability of the product obtained in storage (Table a).
1 pbw Si 167/100 pbw VN3 ~ 1~256 10-7mo1 Si 167/m2 1 pbw Si 189/100 pbw VN3 ~ 2~g09 10-7mo1 A 189/m2 13 9~ 116 xv Chemical analysis modified Ultrasil VtJ3_ O~en storage at 50 C
l sul fur t T
~ o .
a TheoreticalStarting 6 Months 12 Months _pb~rr _A189calculated material _ % o ' 100 pbw VN3 1.1 0.151 0.165 0.180 0.213 2.2 0.323 0.336 0.521 0.530 3.3 0.493 0.550 0.731 0.664 3.8 0.576 0.639 0.739 0.742 4.4 0.659 0.747 1.234 1.205 5.5 0.822 0.918 1.393 1.102 8.2 1.219 1.373 1.858 1.783 10.9 1.599 1.864 2.419 2.051 Table 4 Chemical -analysis - Si167 -modified Ultrasil Open storage at 50C
d ~olysulfide sulfur TheoreticalStarting 6 Months 12 Months lbw Si167 calculated material 100 pbw VN3 0 2.5 pbw Si167 0.324 0.339 0.322 0.300 5.4 pbw Si167 0.635 0.684 0.653 0.620 7.6 pbw Si167 0.934 0.964 0.921 0.950 8.9 pbw Si167 1.079 1.135 1.042 1.004 10.1 pbw Si1671.221 1.237 1.219 1.202 12.7 pbw Si1671.497 1.587 1.473 1.402 Table 5 w 14 90 116 KV
Example 3 Silicas modified with 3-thiocyanatopropyl triethoxy-silane (Si 264) are produced in accordance with Examples 1 and 2. The following values are obtained for the free ethoxy groups on the surface (per silane molecule) Table 6 pEW Si 264/100 PBW VN3 Mol Si264/m2 Ethoxy groups 1.34 3 10' 0.65 2.65 7 10' 0.45 4.02 1 106 0.29 5.4 1.4 106 0.23 6.7 1.8 106 0.24 Table 7 pEW Si 264/100 PEW VN2 Mol Si264/m2 Ethoxy groups 1.34 5 . 10_~ . 0.49 2.65 1 106 0.29 4.02 1.5 106 0.24 5.4 2.0 10 6 0.26 6.7 2.5 106 0.30 ... 1 5 9 0 116 ~;V
Table 8 Precip.i.tar~ed silicamodified with Si264in SBR 1500 Buna Hiils 1500 100 100 100 Zn0 RS 3 3 3 Stearic acid 2 2 2 ULTR1~SIL VPI 2 50 - -Si264 mod. VN2 - 50 -(4.82 pbw Si264 to 100 pbw VN2) Si264 mod. VN2 - - 5U
(6.7 pbw Si264 to 1 00 pbw VN2) Vulkaci_t CZ 2 2 2 Sulfur 2 2 2 Rheometer 150°C
Dmax - Dmin ( Nm ) 9 . 7 9 11. 91 12 .
doz (rains.) 19.1 16.3 14.0 tsox (minx,) 40.3 45.9 36.4 tso z ' do x (mlns. ) 24. 3 29. 6 22.4 Vulcanization temperature: 150C/tssz Tensile strength (MPa) 14.3 26.0 25.7 Modulus, 300 (MPa) 3.8 7.3 8.5 Elongation at at break 650 600 560 (o) Shore hardness 66 76 76
Claims (4)
1. A process for the surface modification of natural or synthetic oxidic or silicate fillers using one or more organosilicon compounds corresponding to formula (I) [R1n(RO)3-n S1-(Alk)m-(Ar)p]q [B] (I) in which B represents -SCN (where q = 1) or -S x- (where q = 2);
R and R1 may be the same or different and represent a C1-4 alkyl group or the phenyl radical, in addition to which R may be a C1-4-alkyl-C1-4-alkoxy group;
n is 0, 1 or 2;
Alk is a difunctional, linear or branched hydrocarbon radical containing 1 to 6 carbon atoms;
m is 0 or 1;
Ar is a C6-12 arylene radical;
p is 0 or 1, with the proviso that p and m cannot both be 0; and x is a number of 2 to 8;
wherein:
a) at least one organosilicon compound corresponding to formula I is intensively mixed with the filler at temperatures below 60°C in a concentration of 1 x 10-7 to 3.5 x 10-6 mol trialkoxysilyl groups per square meter filler surface, to form a homogenized mixture, and b) the homogenized mixture is then subjected to a hydrophobicizing reaction in a preheated mixer, in a constant-temperature bed or in any other suitable heatable reaction vessel at a temperature of 60 to 160°C.
R and R1 may be the same or different and represent a C1-4 alkyl group or the phenyl radical, in addition to which R may be a C1-4-alkyl-C1-4-alkoxy group;
n is 0, 1 or 2;
Alk is a difunctional, linear or branched hydrocarbon radical containing 1 to 6 carbon atoms;
m is 0 or 1;
Ar is a C6-12 arylene radical;
p is 0 or 1, with the proviso that p and m cannot both be 0; and x is a number of 2 to 8;
wherein:
a) at least one organosilicon compound corresponding to formula I is intensively mixed with the filler at temperatures below 60°C in a concentration of 1 x 10-7 to 3.5 x 10-6 mol trialkoxysilyl groups per square meter filler surface, to form a homogenized mixture, and b) the homogenized mixture is then subjected to a hydrophobicizing reaction in a preheated mixer, in a constant-temperature bed or in any other suitable heatable reaction vessel at a temperature of 60 to 160°C.
2. A method for the surface-modification of natural or synthetic, oxide or silicate fillers having surface -OH
groups using one or more organosilicon compounds of the Formula I:
[R1n(RO)3-n Si-(Alk)m-(Ar)p]q [B] (I) in which:
B represents -SCN (if q=1) or -S x - (if q=2) ;
R signifies an alkyl croup with 1 to 4 carbon atoms, the phenyl group, or a C1-C4 alkyl-C1-C4 alkoxy group;
R1 signifies an alkyl group with 1 to 4 carbon atoms or the phenyl group;
n represents 0, 1 and 2;
Alk signifies a bivalent, straight or branched hydrocarbon group having 1 to 6 carbon atoms;
m represents 0 or 1;
Ar is an arylene group with 6 to 12 carbon atoms;
p is 0 or 1, with the provision that p and m do not signify 0 simultaneously; and x is a number from 2 to 8;
said method comprising:
a) intensively mixing at least one organosilicon compound according to Formula I with the filler, but without the addition of further solvents, at a temperature below 60°C in a concentration of up to 3.5 x 10-6 moles trialkoxysilyl groups per one square meter filler surface, to form a homogenized mixture, and b) subsequently subjecting the homogenized mixture to a hydrophobing reaction at temperature greater than 60°C.
groups using one or more organosilicon compounds of the Formula I:
[R1n(RO)3-n Si-(Alk)m-(Ar)p]q [B] (I) in which:
B represents -SCN (if q=1) or -S x - (if q=2) ;
R signifies an alkyl croup with 1 to 4 carbon atoms, the phenyl group, or a C1-C4 alkyl-C1-C4 alkoxy group;
R1 signifies an alkyl group with 1 to 4 carbon atoms or the phenyl group;
n represents 0, 1 and 2;
Alk signifies a bivalent, straight or branched hydrocarbon group having 1 to 6 carbon atoms;
m represents 0 or 1;
Ar is an arylene group with 6 to 12 carbon atoms;
p is 0 or 1, with the provision that p and m do not signify 0 simultaneously; and x is a number from 2 to 8;
said method comprising:
a) intensively mixing at least one organosilicon compound according to Formula I with the filler, but without the addition of further solvents, at a temperature below 60°C in a concentration of up to 3.5 x 10-6 moles trialkoxysilyl groups per one square meter filler surface, to form a homogenized mixture, and b) subsequently subjecting the homogenized mixture to a hydrophobing reaction at temperature greater than 60°C.
3. A method for the surface-modification of natural or synthetic, oxide or silicate fillers having surface -OH
groups using one or more organosilicon compounds of the Formula I:
[R1n(RO)3-n Si- (Alk)m-(Ar)p]q [B] (I) in which:
B represents -SCN (if q=1) or -S x - (if q=2) ;
R signifies an alkyl group with 1 to 4 carbon atoms, the phenyl group, or a C1-C4 alkyl-C1-C4 alkoxy group;
R1 signifies an alkyl group with 1 to 4 carbon atoms or the phenyl group;
n represents 0, 1 and 2;
Alk signifies a bivalent, straight or branched hydrocarbon group having 1 to 6 carbon atoms;
m represents 0 or 1;
Ar is an arylene group with 6 to 12 carbon atoms;
p is 0 or 1, with the provision that p and m do not signify 0 simultaneously; and x is a number from 2 to 8;
said method comprising:
a) intensively mixing at least one organosilicon compound according to Formula I with the filler, but without the addition of further solvents, at a temperature below 60°C in a concentration of 1 x 10-7 to 3.5 x 10-6 moles trialkoxysilyl groups per one square' meter filler surface to form a homogenized mixture, and b) subsequently subjecting the homogenized mixture to a hydrophobing reaction at temperature of 60 to 160°C.
groups using one or more organosilicon compounds of the Formula I:
[R1n(RO)3-n Si- (Alk)m-(Ar)p]q [B] (I) in which:
B represents -SCN (if q=1) or -S x - (if q=2) ;
R signifies an alkyl group with 1 to 4 carbon atoms, the phenyl group, or a C1-C4 alkyl-C1-C4 alkoxy group;
R1 signifies an alkyl group with 1 to 4 carbon atoms or the phenyl group;
n represents 0, 1 and 2;
Alk signifies a bivalent, straight or branched hydrocarbon group having 1 to 6 carbon atoms;
m represents 0 or 1;
Ar is an arylene group with 6 to 12 carbon atoms;
p is 0 or 1, with the provision that p and m do not signify 0 simultaneously; and x is a number from 2 to 8;
said method comprising:
a) intensively mixing at least one organosilicon compound according to Formula I with the filler, but without the addition of further solvents, at a temperature below 60°C in a concentration of 1 x 10-7 to 3.5 x 10-6 moles trialkoxysilyl groups per one square' meter filler surface to form a homogenized mixture, and b) subsequently subjecting the homogenized mixture to a hydrophobing reaction at temperature of 60 to 160°C.
4. A process as set forth in claim 2 or 3, in which said organosilicon compound is bis(3-trimethoxysilyl-propyl)tetrasulfane.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4004781.4 | 1990-02-16 | ||
| DE4004781A DE4004781A1 (en) | 1990-02-16 | 1990-02-16 | Modifying surface of natural or synthetic oxidic or silicate fillers - using organo:silicon cpds. useful in vulcanisable natural rubber mixts. to improve rubber properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2036488A1 CA2036488A1 (en) | 1991-08-17 |
| CA2036488C true CA2036488C (en) | 2002-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002036488A Expired - Fee Related CA2036488C (en) | 1990-02-16 | 1991-02-15 | A process for the production of fillers modified with organosilicon compounds, the fillers thus modified and their use |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5116886A (en) |
| EP (1) | EP0442143B1 (en) |
| JP (1) | JP3019167B2 (en) |
| KR (1) | KR100202797B1 (en) |
| CN (1) | CN1040010C (en) |
| AT (1) | ATE98662T1 (en) |
| BR (1) | BR9100561A (en) |
| CA (1) | CA2036488C (en) |
| DE (2) | DE4004781A1 (en) |
| DK (1) | DK0442143T3 (en) |
| ES (1) | ES2062288T3 (en) |
| MX (1) | MX173875B (en) |
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| DE4236218C2 (en) * | 1991-12-19 | 2001-08-16 | Degussa | Vulcanizable EPDM rubber compounds |
| JPH0620363A (en) | 1992-05-15 | 1994-01-28 | Hewlett Packard Co <Hp> | Auto-changer |
| US5723529A (en) * | 1994-12-21 | 1998-03-03 | The Goodyear Tire & Rubber Company | Silica based aggregates, elastomers reinforced therewith and tire tread thereof |
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| IN188702B (en) * | 1995-06-01 | 2002-10-26 | Degussa | |
| US5780531A (en) * | 1995-06-28 | 1998-07-14 | Bayer Ag | Surface-modified, oxidic or siliceous fillers and their use |
| WO1997007165A1 (en) * | 1995-08-16 | 1997-02-27 | Osi Specialties, Inc. | Stable silane compositions on silica carrier |
| MX9603304A (en) * | 1995-09-23 | 1997-03-29 | Degussa | Process for the production of vulcanizable rubber mixtures. |
| DE19609619A1 (en) * | 1996-03-12 | 1997-09-18 | Degussa | Low-dust, easily dispersible granules based on silicate fillers modified with organosilicon compounds |
| DE19621462A1 (en) * | 1996-05-29 | 1997-12-04 | Degussa | Mixtures consisting of finely divided feldspar and organosilicon compounds, their production and use |
| CA2264722A1 (en) * | 1996-09-02 | 1998-03-12 | Sanyo Trading Co., Ltd. | Silane-treated clay production method, silane-treated clay and composition containing same |
| JPH1088028A (en) * | 1996-09-02 | 1998-04-07 | J M Huber Corp | Silane-treated clay product, preparation thereof, and composition thereof |
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| US5840795A (en) * | 1997-04-30 | 1998-11-24 | J. M. Huber Corporation | Treated clay product, methods of making and using and products therefrom |
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| DE19858706A1 (en) * | 1998-12-18 | 2000-06-21 | Pulver Kautschuk Union Gmbh | Rubber powder (compounds) and process for their preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4076550A (en) * | 1971-08-17 | 1978-02-28 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler | Reinforcing additive |
| CA1046681A (en) * | 1974-06-25 | 1979-01-16 | Union Carbide Corporation | Mercapto-silane coupler-inorganic powder mixtures |
| DE3314742C2 (en) * | 1983-04-23 | 1987-04-02 | Degussa Ag, 6000 Frankfurt | Process for the preparation of surface-modified natural, oxidic or silicate fillers and their use |
| DE3437473A1 (en) * | 1984-10-12 | 1986-04-17 | Degussa Ag, 6000 Frankfurt | SYNTHETIC, SILICATIC FILLERS MODIFIED ON THE SURFACE, A METHOD FOR THE PRODUCTION AND THE USE THEREOF |
| GB2206889B (en) * | 1987-06-11 | 1991-03-20 | Asics Corp | Rubber composition and golf ball comprising it |
| JP2588734B2 (en) * | 1987-11-25 | 1997-03-12 | 昭和電線電纜株式会社 | Arc resistant electrical insulation composition |
-
1990
- 1990-02-16 DE DE4004781A patent/DE4004781A1/en not_active Withdrawn
- 1990-12-24 EP EP90125475A patent/EP0442143B1/en not_active Expired - Lifetime
- 1990-12-24 DK DK90125475.5T patent/DK0442143T3/en active
- 1990-12-24 DE DE90125475T patent/DE59003893D1/en not_active Expired - Lifetime
- 1990-12-24 AT AT90125475T patent/ATE98662T1/en not_active IP Right Cessation
- 1990-12-24 ES ES90125475T patent/ES2062288T3/en not_active Expired - Lifetime
-
1991
- 1991-02-08 BR BR919100561A patent/BR9100561A/en not_active Application Discontinuation
- 1991-02-11 MX MX024485A patent/MX173875B/en unknown
- 1991-02-12 KR KR1019910002312A patent/KR100202797B1/en not_active IP Right Cessation
- 1991-02-13 CN CN91100906A patent/CN1040010C/en not_active Expired - Lifetime
- 1991-02-14 JP JP3020872A patent/JP3019167B2/en not_active Expired - Lifetime
- 1991-02-15 CA CA002036488A patent/CA2036488C/en not_active Expired - Fee Related
- 1991-02-15 US US07/655,780 patent/US5116886A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0517705A (en) | 1993-01-26 |
| ATE98662T1 (en) | 1994-01-15 |
| DK0442143T3 (en) | 1994-04-18 |
| MX173875B (en) | 1994-04-07 |
| EP0442143A1 (en) | 1991-08-21 |
| KR910015640A (en) | 1991-09-30 |
| DE4004781A1 (en) | 1991-08-22 |
| BR9100561A (en) | 1991-10-29 |
| CA2036488A1 (en) | 1991-08-17 |
| ES2062288T3 (en) | 1994-12-16 |
| DE59003893D1 (en) | 1994-01-27 |
| JP3019167B2 (en) | 2000-03-13 |
| CN1054089A (en) | 1991-08-28 |
| EP0442143B1 (en) | 1993-12-15 |
| CN1040010C (en) | 1998-09-30 |
| US5116886A (en) | 1992-05-26 |
| KR100202797B1 (en) | 1999-06-15 |
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